Co-pyrolysis of refinery oil sludge with biomass and spent fluid catalytic cracking catalyst for resource recovery.

Catalytic co-pyrolysis of two different refinery oily sludge (ROS) samples was conducted to facilitate resource recovery. Non-catalytic pyrolysis in temperatures ranging from 500 to 600°C was performed to determine high oil yields. Higher temperatures enhanced the oil yields up to ~ 24 wt%, while char formation remained unchanged (~ 45%) for S1. Conversely, S2 exhibited a notably lower oil yield (~ 4 wt%) than S1. Pyrolysis oil of S1 consisted of phenolics (~ 50% at 600 °C) whereas hydrocarbons were predominant in S2 oil (~ 80% at 600 °C). Catalytic pyrolysis of S1 did not exhibit a substantial impact on oil yields but the oil composition varied significantly. High hydrocarbons, phenolics, and aromatics were obtained with molecular sieve (MS), metal slag, and ZSM-5, respectively. Catalytic co-pyrolysis of S2 with sawdust (SD) in the presence of MS enhanced the oil yield, and the resulting oil consisted of high hydrocarbons (~ 54%) and aromatics (~ 44%).

Atomically Dispersed Iron-Copper Dual-Metal Sites Synergistically Boost Carbonylation of Methane.

The direct liquid-phase oxidative carbonylation of methane, utilizing abundant natural gas, offers a mild and straightforward alternative. However, most catalysts proposed for this process suffer from low acetic acid yields due to few active sites and rapid C1 oxygenate generation, impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe-HZSM-5-TF (TF denotes template-free synthesis) catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM-5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat -1 h-1 at 50 °C, tripling the previous records of 12.0 mmol gcat -1 h-1. Comprehensive characterization, isotope-labeled experiments and density functional theory (DFT) calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process, promoting C-C coupling for effective acetic acid synthesis. Furthermore, the methyl-group carbon in acetic acid originates solely from methane, while its carbonyl-group carbon is derived exclusively from CO, rather than the conversion of other C1 oxygenates. The proposed bimetallic catalyst design not only overcomes the limitations of current catalysts but also generalizes the oxidative carbonylation of other alkanes, demonstrating promising advancements in sustainable chemical synthesis.

The stabilization ability of NaA zeolite derived from fly ash for lead and cadmium in soil: Mechanisms and evaluation of effectiveness.

Developing technologies aimed at ecologically restoring is of great significance in addressing the problem of heavy metal pollution. In this study, NaA zeolites (FAZ) originated from fly ash with outstanding performance were prepared by alkali fusion hydrothermal method and used for the solidification and stabilization of heavy metals in soil. After systematic evaluation, it was found that FAZ may lower the leaching concentration of lead (Pb) in soil to <1 mg/kg and increase the stabilization rate of Pb to 80 % in the single Pb-contaminated soil, lower the leaching concentration of cadmium (Cd) in soil to <3 mg/kg and increase the stabilization rate of Cd to 60 % in the single Cd-contaminated soil, and lower the leaching concentration of Pb to 0.15 mg/kg and the leaching concentration of Cd to 0.74 mg/kg in PbCd complex polluted soil. Additionally, Pb stabilization rates reach 60 % and Cd stabilization rates reach 30 %, respectively. Ion exchange is primarily responsible for the adsorption and solidification of Pb and Cd in soil by FAZ. Generally, FAZ has a wide range of applications in the rehabilitation of contaminated soil and significantly lowers the level of heavy metal pollution in soil.

Enhancing the bioavailability and activity of natural antioxidants with nanobubbles and nanoparticles.

KEY POLICY HIGHLIGHTSNanobubbles and nanoparticles may enhance the polyphenols' bioavailabilityNanobubbles may stimulate the activation of Nrf2 and detox enzymesArmoured oxygen nanobubbles may enhance radiotherapy or chemotherapy effects.

Influence of Chabazite Zeolite Foliar Applications Used for Olive Fruit Fly Control on Volatile Organic Compound Emission, Photosynthesis, and Quality of Extra Virgin Olive Oil.

The olive fruit fly (Bactrocera oleae Rossi) is the most dangerous pest of olive fruits and negatively influences the chemical and sensory quality of the oil produced. Organic farms have few tools against this pest and are constantly looking for effective and sustainable products such as geomaterials, i.e., zeolite. Since a particle film covers the canopy, a study was carried out on the olive tree's responses to zeolite foliar coating. The tested treatments were natural zeolite (NZ), zeolite enriched with ammonium (EZ), and Spintor-Fly® (SF). EZ was associated with higher photosynthetic activity with respect to the other treatments, while no differences were found between SF and NZ. Foliar treatments affect the amount of BVOC produced in both leaves and olives, where 26 and 23 different BVOCs (biogenic volatile organic compounds) were identified but not the type of compounds emitted. Foliar treatment with EZ significantly affected fruit size, and the olive fruit fly more frequently attacked the olives, while treatment with NZ had olives with similar size and attack as those treated with Spintor-Fly®; no difference in oil quantity was detected. Oil produced from olives treated with NZ presented higher values of phenolic content and intensities of bitterness and spiciness than oils from those treated with EZ and SF. According to the results of this study, using zeolite films on an olive tree canopy does not negatively influence plant physiology; it has an impact on BVOC emission and the chemical and sensory characteristics of the oil.

Bolivian natural zeolite as a low-cost adsorbent for the adsorption of cadmium: Isotherms and kinetics.

Population growth in recent years has led to increased wastewater production and pollution of water resources. This situation also heavily affects Bolivia, so wastewater treatment methods and materials suitable for Bolivian society should be explored. This study investigated the natural Bolivian Zeolite (BZ) and its NaCl-modified structure (NaBZ) as adsorbents for cadmium removal from water. The natural BZ and the modified form NaBZ were investigated by different physicochemical characterization techniques. Furthermore, XPS and FT-IR techniques were used to investigate the adsorption mechanisms. The cadmium adsorption on BZ and NaBZ was analyzed using various mathematical models, and the Langmuir model provided a better description of the experimental adsorption data with cadmium adsorption capacities of 20.2 and 25.6 mg/g for BZ and NaBZ, respectively. The adsorption followed the pseudo-second order kinetics. The effect of different parameters, such as initial cadmium concentration and pH on the adsorption was studied. In addition, the results of the regeneration test indicated that both BZ and NaBZ can be regenerated by using hydrochloric acid (HCl). Finally, the adsorption experiment of BZ and NaBZ on a real water sample (brine from Salar de Uyuni salt flat) containing a mixture of different heavy metals was carried out. The results obtained in this study demonstrate the effectiveness of natural BZ and modified NaBZ in the removal of heavy metals from wastewater.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia 3 ‾ ${\bar{3}}$ d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Nature and Redox Properties of Iron Sites in Zeolites Revealed by Mössbauer Spectroscopy.

Iron-containing zeolite-based catalysts play a pivotal role in environmental processes aimed at mitigating the release of harmful greenhouse gases, such as nitrous oxide (N2 O) and methane (CH4 ). Despite the rich iron chemistry in zeolites, only a fraction of iron species that exhibit an open coordination sphere and possess the ability for electron transfer are responsible for activating reagents. In addition, the splitting of molecular oxygen is facilitated by bare iron cations embedded in zeolitic matrices. Mössbauer spectroscopy is the ideal tool for investigating the valency and geometry of iron species in zeolites because it leaves no iron forms silent and provides insights into in-situ processes. This review is dedicated to the utilization of Mössbauer spectroscopy to elucidate the nature of the extra-framework iron centers in ferrierite (FER), beta-structured (*BEA), and ZSM-5 zeolite (MFI) zeolites, which are active in N2 O decomposition and CH4 oxidation through using the active oxygen derived from N2 O and O2 . In this work, a structured summary of the Mössbauer parameters established over the last two decades is presented, characterizing the specific iron active centers and intermediates formed upon iron's interaction with N2 O/O2 and CH4 . Additionally, the impact of preparation methods, iron loading, and the long-term stability on iron speciation and its redox behavior under reaction conditions is discussed.

Continuous Anhydrous Synthesis of Oxymethylene Dimethyl Ethers by Reaction of Dimethyl Ether with Molecular Formaldehyde.

A novel gaseous synthesis route to oxymethylene dimethyl ethers (OMEn, n = 3-5) starting from CO2 and green H2 by using molecular formaldehyde (FA) and dimethyl ether (DME) is presented. The anhydrous reaction runs in a pressure free, gaseous, and continuous reaction setup. Hetero-geneous cata-lysts including zeolites and ion exchange resins (IER) are investigated, if they catalyze this reaction. While IER is almost inactive, zeolites with a 3D pore structure and an acidity exceeding ρm,H+ (NH3,ads ) = 250 µmol·gcat.-1 proved to be catalytically active. DME conversions of up to 2.76 mol-% are observed. The observed product gas stream compositions confirm thermo-dynamic considerations with back reactions / OMEn decomposition occurring as part of the equilibria under the investigated reaction conditions (90…180 °C). However, feed gas ratio variations (FA:DME = 1:2 to 1:9.5) highlighted the possibility to shift the product selectivity in favor of OMEn and suppress FA disproportionation to methyl formate. FA trimerization to trioxane is almost completely suppressed by running the reaction at 120 °C. The results presented here provide an important and unprecedented contribution to understand the complex reaction network in the OMEn synthesis reaction necessary to establish an energy efficient sustainable OMEn production process.

Hollow STW-Type Zeolite Single Crystals with Aluminum Gradient for Highly Selective Production of p-Xylene from Methanol-Toluene Alkylation.

Zeolites with uniform micropores are important shape-selective catalysts. However, the external acid sites of zeolites have a negative impact on shape-selective catalysis, and the microporosity may lead to serious diffusion limitation. Herein, we report on the direct synthesis of hierarchical hollow STW-type zeolite single crystals with a siliceous exterior. In an alkalinous fluoride medium, the nucleation of highly siliceous STW zeolites takes place first, and the nanocrystals are preferentially aligned on the outer surface of the gel agglomerates to grow into single crystalline shells upon crystallization. The lagged crystallization of the internal Al-rich amorphous gels onto the inner surface of nanocrystalline zeolite shells leads to the formation of hollow cavities in the core of the zeolite crystals. The hollow zeolite single crystals possess a low-to-high aluminum gradient from the surface to the core, resulting in an intrinsic inert external surface, and exhibit superior catalytic performance in toluene methylation reactions.

Revealing Active Sites and Reaction Pathways in Methane Non-Oxidative Coupling over Iron-Containing Zeolites.

Non-oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas-phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X-ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3-butadiene, 2-butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small-pore [Fe]CHA, where ethylene and ethane are the only gas-phase products.

Dynamical Equilibrium between Brønsted and Lewis Sites in Zeolites: Framework-Associated Octahedral Aluminum.

While the structures of Brønsted acid sites (BAS) in zeolites are well understood, those of Lewis acid sites (LAS) remain an active area of investigation. Under hydrated conditions, the reversible formation of framework-associated octahedral aluminum has been observed in zeolites in the acidic form. However, the structure and formation mechanisms are currently unknown. In this work, combined experimental 27 Al NMR spectroscopy and computational data reveal for the first time the details of the zeolite framework-associated octahedral aluminium. The octahedral LAS site becomes kinetically allowed and thermodynamically stable under wet conditions in the presence of multiple nearby BAS sites. The critical condition for the existence of such octahedral LAS appears to be the availability of three protons: at lower proton concentration, either by increasing the Si/Al or by ion-exchange to non-acidic form, the tetrahedral BAS becomes thermodynamically more stable. This work resolves the question about the nature and reversibility of framework-associated octahedral aluminium in zeolites.

Development of High Temperature Water Sorbents Based on Zeolites, Dolomite, Lanthanum Oxide and Coke.

Methanation is gaining attention as it produces green methane from CO2 and H2, through Power-to-Gas technology. This process could be improved by in situ water sorption. The main difficulty for this process intensification is to find effective water sorbents at useful reaction temperatures (275-400 °C). The present work comprises the study of the water sorption capacity of different materials at 25-400 °C. The sorption capacity of the most studied solid sorbents (zeolites 3A & 4A) was compared to other materials such as dolomite, La2O3 and cokes. In trying to improve their stability and sorption capacity at high temperatures, all these materials were modified with alkaline-earth metals (Ba, Ca & Mg). Lanthana-Ba and dolomite sorbents were the most promising materials, reaching water sorption values of 120 and 102 mgH2O/gsorbent, respectively, even at 300 °C, i.e., values 10-times higher than the achieved ones with zeolites 3A or 4A under the same operating conditions. At these high temperatures, around 300 °C, the water sorption process was concluded to be closer to chemisorption than to physisorption.

Combining Zeolites with Early-Maturing Annual Legume Cover Crops in Rainfed Orchards: Effects on Yield, Fatty Acid Composition and Polyphenolic Profile of Olives and Olive Oil.

Under climate change threats, there is a growing need to adapt the conventional agronomic practices used in rainfed olive orchards by sustainable practices, in order to ensure adequate crop yield and olive oil quality and to preserve soil health. Therefore, for two years, the effects of conventional tillage practice (T) and two sustainable soil management strategies, a leguminous cover crop (LC) and its combination with natural zeolites (ZL), on the yield, fatty acid composition, polyphenolic profile and quality indices of olive fruits and oil were evaluated. Crop yield was significantly increased by LC and ZL in the first year. Although in the second year no significant differences were verified, the cumulative yield increased significantly by 31.6% and 35.5% in LC and ZL trees, respectively. LC enhanced the moisture and size of olives, while ZL increased, in general, the concentrations of oleuropein, verbascoside, caffeic acid and epicatechin, as well the oleic/linoleic ratio in fruits and the levels of 3,4-dihydroxyphenylglycol, tyrosol, verbascoside and caffeic acid in olive oil. Despite the higher concentration of total phenols in the fruits and oil from T trees in the warmer and dryer year, the quality of the oil decreased, mainly when compared with ZL, as evidenced by the peroxide value and K232 and K270 coefficients. In short, both sustainable soil management strategies appear to be promising practices to implement in olive orchards under rainfed conditions, but the innovative strategy of combining zeolites with legume cover crops, first reported in the present study, confers advantages from a nutritional and technological point of view. Nevertheless, studies subjected to the long-term use of these practices should be conducted to ensure the sustainability of the crop yield and olive oil quality.

Synthesis and Characterization of Hierarchical Zeolites Modified with Polysaccharides and Its Potential Role as a Platform for Drug Delivery.

Hierarchical zeolites are aluminosilicates with a crystal structure, which next to the micropores possess secondary porosity in the range of mesopores and/or small macropores. Due to their ordered structure and additional secondary porosity, they have aroused great interest among scientists in recent years. Therefore, the present work concerns the synthesis and characterization of hierarchical zeolites with secondary mesoporosity, based on commercial zeolites such as MFI (ZSM-5), BEA (ß) and FAU (Y), and modified with polysaccharides such as inulin, hyaluronic acid, and heparin. All materials were characterized by various analytical techniques and applied as a platform for delivery of selected drug molecules. On the basis of X-ray diffraction (presence of reflections in the 2θ angle range of 1.5-2.5°) and low-temperature nitrogen sorption isotherms (mixture of isotherms of I and IV type) additional secondary porosity was found in the mesopore range. Additional tests were also conducted to determine the possibility of loading selected molecules with biological activity into the aforementioned materials and then releasing them in the therapeutic process. Molecules with different therapeutic options were selected for testing, namely ibuprofen, curcumin, and ferulic acid with anti-inflammatory, potentially anticancer, antioxidant, and skin discoloration activities, respectively. Preliminary studies have confirmed the possibility of using hierarchical zeolites as potential carriers for bioactive molecules, as the loading percentage of active substances ranged from 39-79% and cumulative release for ibuprofen reached almost 100% after 8 h of testing.

Resource recovery from discarded COVID-19 PPE kit through catalytic fast pyrolysis.

During the COVID-19 pandemic, the world saw an exponential surge in the production of Personal Protective Equipment (PPE) kits, which eventually got discarded in the biomedical waste stream. In this study, thirteen different polymer samples from the PPE kit were collected and characterized using Fourier transform infrared spectrometer, thermogravimetric analysis, and analytical pyrolysis-gas chromatograph/mass spectrometry. The characterization data showed that about 94 % by mass of components were made of only three polymers, viz. polypropylene (PP, 75.6 wt %), polyethylene terephthalate (PET, 12.5 wt %), and polycarbonate (PC, 6 wt %). The analytical pyrolysis of the PPE coverall suit (PP) yielded mainly alkenes containing 2,4-dimethyl-1-heptene as the major compound with 17 wt % yield at 600 °C. The pyrolysates from face shield (PET) were rich in benzoic acid (5.8 wt %) and acetophenone (4.8 wt %), while those from safety goggles (PC) were rich in phenol (17.6 wt %) and p-cresol (12.4 wt %) at 600 °C. HZSM-5 and HY zeolites were used for the catalytic upgradation of pyrolysates especially from PP, PET and PC. The temperature and feed-to-catalyst ratio were optimized by performing catalytic fast pyrolysis experiments at 500 °C, 600 °C and 700 °C with different feed-to-catalyst ratios 1:2, 1:4, and 1:6 (w/w). The yield of aromatic hydrocarbons, viz., BTEX (benzene, toluene, ethylbenzene, xylenes) and naphthalene, was maximum (∼25.7 wt %) from PP coverall when HY catalyst was used at 600 °C and 1:6 (w/w) loading. In the case of PET face shield, the total yield of BTEX, naphthalene and biphenyl was maximum (27.9 wt %) at 600 °C and 1:4 (w/w) of HZSM-5, while in the case of PC goggles, it was maximum (18.6 wt %) at 700 °C and 1:4 (w/w) of HY. This study shows that the entire PPE kit can be valorized via catalytic fast pyrolysis to generate petrochemical products and platform molecules like monoaromatic hydrocarbons at high selectivities.

Investigation of the Effect of Zeolite Supports and the Role of W-Species for One-Pot Catalytic Conversion of Cellulose to Ethylene Glycol: Theoretical & Experimental Studies.

Endeavors were made to study the influence of various zeolite (HY, NaY, NaZSM-5 and HZSM-5) supports with (Al)-Ni-W metal combination catalysts for the ethylene glycol (EG) production, selectively from cellulose. From the experimental results ZSM-5 (NaZSM-5/73.3% & HZSM-5/67.7%) support is superior over HY & NaY support in selective EG production from cellulose. It was understood that W- species with oxygen vacancies (WO3-x , XPS analysis) plays an important role in producing the glycolaldehyde (GA) intermediate (via C-C cleavages), which on hydrogenation over Ni- sites selectively produce EG. Further, the studies based on the Density Functional Theory (DFT) were conducted to substantiate the involvement of the WO3-x species in the reaction. The adsorption energies and structural changes establish that the C2 -C3 bond of the glucose elongates and thereby activates on adsorbing to WO3-x sites supporting the formation of GA. Activation of GA on Ni- sites is distinguished by an increase of 0.1 Šin C=O bond length, which facilitates the hydrogenation of C=O resulting in EG. The reaction pathway is explained through an analysis of CDD and DOS.

Impact of Mineralizing Agents on Aluminum Distribution and Acidity of ZSM-5 Zeolites.

Intensive research on improving the catalytic properties of zeolites is focused on modulating their acidity and the distribution of associated Al sites. Herein, by studying a series of ZSM-5 zeolites over a broad range of Al content, we demonstrate how the nature of the mineralizing agent (F- or OH- ) used in hydrothermal syntheses directly impacts Al sites distribution. The proportions of Al sites, probed by 27 Al NMR, depend on the Si/Al ratio for F- , but remain identical for OH- (from Si/Al=30 to 760). This leads to contrasting variations in weak and strong acidities. Such opposite effect of mineralizers is explained by the spatial location of negative charges and the resulting balance between short- and long-range electrostatic interactions. This understanding paves the way for additional and simple opportunities to control zeolites' acidity.

Physico-Chemical Modifications Affecting the Activity and Stability of Cu-Based Hybrid Catalysts during the Direct Hydrogenation of Carbon Dioxide into Dimethyl-Ether.

The direct hydrogenation of CO2 into dimethyl-ether (DME) has been studied in the presence of ferrierite-based CuZnZr hybrid catalysts. The samples were synthetized with three different techniques and two oxides/zeolite mass ratios. All the samples (calcined and spent) were properly characterized with different physico-chemical techniques for determining the textural and morphological nature of the catalytic surface. The experimental campaign was carried out in a fixed bed reactor at 2.5 MPa and stoichiometric H2/CO2 molar ratio, by varying both the reaction temperature (200-300 °C) and the spatial velocity (6.7-20.0 NL∙gcat-1∙h-1). Activity tests evidenced a superior activity of catalysts at a higher oxides/zeolite weight ratio, with a maximum DME yield as high as 4.5% (58.9 mgDME∙gcat-1∙h-1) exhibited by the sample prepared by gel-oxalate coprecipitation. At lower oxide/zeolite mass ratios, the catalysts prepared by impregnation and coprecipitation exhibited comparable DME productivity, whereas the physically mixed sample showed a high activity in CO2 hydrogenation but a low selectivity toward methanol and DME, ascribed to a minor synergy between the metal-oxide sites and the acid sites of the zeolite. Durability tests highlighted a progressive loss in activity with time on stream, mainly associated to the detrimental modifications under the adopted experimental conditions.

Catalytic pyrolysis of biomass over zeolites for bio-oil and chemical production: A review on their structure, porosity and acidity co-relation.

The oxygenated compounds found in bio-oil limit their application as a transportation fuel. Several studies were reported on eliminating the oxygenated components from bio-oil so as to improve its fuel properties. This work is dedicated to studying the shape selectivity, porosity, structure, acidity of zeolites and their effect in bio-oil and chemicals production. The unified pore size, specific structure, controlled Si/Al ratio, unique channels and circular entrances, mesoporosity, and acidity are the utmost discerning parameters for aromatics production and deoxygenation reaction. The conversion of biomass-derived oxygenates to aromatics using zeolite is subjected to the reactants entering the pore, conversion inside the pore, and diffusing out of the products from the zeolite pores. These approaches were considered for an in-depth understanding of zeolite properties, which will enhance the fundamental understanding of pyrolysis.